CN103946293B - As alkyl semicarbazone or the dialkyl group semicarbazone of the solidifying agent of epoxy resin - Google Patents
As alkyl semicarbazone or the dialkyl group semicarbazone of the solidifying agent of epoxy resin Download PDFInfo
- Publication number
- CN103946293B CN103946293B CN201280055597.9A CN201280055597A CN103946293B CN 103946293 B CN103946293 B CN 103946293B CN 201280055597 A CN201280055597 A CN 201280055597A CN 103946293 B CN103946293 B CN 103946293B
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- China
- Prior art keywords
- epoxy resin
- semicarbazone
- cycloalkyl
- branching
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 157
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 157
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 90
- 150000007659 semicarbazones Chemical class 0.000 title claims abstract description 63
- -1 alkyl semicarbazone Chemical class 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 130
- 238000000034 method Methods 0.000 claims abstract description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 238000007711 solidification Methods 0.000 claims description 29
- 230000008023 solidification Effects 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- 125000001118 alkylidene group Chemical group 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 6
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 4
- FCFXPDZISVZNJB-UHFFFAOYSA-N 3-(cyclopentylideneamino)-1,1-dimethylurea Chemical compound CN(C)C(=O)NN=C1CCCC1 FCFXPDZISVZNJB-UHFFFAOYSA-N 0.000 claims description 4
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- AJBXRBRVQMZREG-UHFFFAOYSA-N OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC Chemical compound OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC AJBXRBRVQMZREG-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- YZRWCYUQZHRZMD-UHFFFAOYSA-N 1,1-dimethyl-3-(propan-2-ylideneamino)urea Chemical compound CN(C)C(=O)NN=C(C)C YZRWCYUQZHRZMD-UHFFFAOYSA-N 0.000 claims description 3
- UIBBSRGDMJYFAK-UHFFFAOYSA-N 3-(butan-2-ylideneamino)-1,1-dimethylurea Chemical compound CCC(C)=NNC(=O)N(C)C UIBBSRGDMJYFAK-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- PVWJZBUMBQDHEJ-UHFFFAOYSA-N 1,1-diethyl-3-(propan-2-ylideneamino)urea Chemical compound CCN(CC)C(=O)NN=C(C)C PVWJZBUMBQDHEJ-UHFFFAOYSA-N 0.000 claims description 2
- GMVWXZPAXSIJGS-UHFFFAOYSA-N 3-(cyclopentylideneamino)-1,1-diethylurea Chemical compound CCN(CC)C(=O)NN=C1CCCC1 GMVWXZPAXSIJGS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- PGPFRBIKUWKSTJ-UHFFFAOYSA-N cyclopropylcyclopropane Chemical group C1CC1C1CC1 PGPFRBIKUWKSTJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 2
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000003685 thermal hair damage Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000010412 perfusion Effects 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- JISVIRFOSOKJIU-UHFFFAOYSA-N hexylidene Chemical group [CH2+]CCCC[CH-] JISVIRFOSOKJIU-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/30—Hydrazones; Semicarbazones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2951—Coating or impregnation contains epoxy polymer or copolymer or polyether
Abstract
The present invention relates to alkyl semicarbazone or dialkyl group semicarbazone as solidifying agent for the purposes of cured epoxy resin and the method for controllably cured epoxy resin and composition epoxy resin.
Description
The present invention relates to alkyl semicarbazone or dialkyl group semicarbazone as solidifying agent for the purposes of cured epoxy resin and the method for controllably Cured epoxy resin compositions and composition epoxy resin.
Due to the chemical resistant properties that thermosetting epoxy resin is good, fabulous thermal characteristics and dynamic properties and high electrical isolation capabilities thereof, thermosetting epoxy resin is widely used.In addition, epoxy resin demonstrates good bonding and is therefore particularly suitable for being used in fibre composite (matrix material) on many materials.In order to be used in fibre composite, well moistening (namely for the preparation of the low viscosity of the resin formulation selected by matrix material) of fiber and high mechanical property are desirable.
In order to prepare moulded piece by fibre composite, use diverse ways, such as preimpregnation method, different method for filling or injecting method, particularly RTM-method (resin transfer molding).In these methods, particularly method for filling or injecting method are significant in the past few years.Therefore such as in method for filling, be wherein arranged in the dry reinforcement material of chunk, such as fibrefelt, non-woven fabric, yarn fabric or knitted fabrics, covered by stopping property vacuum diaphragm and flooded by divider passage resin formulations after applying vacuum.The advantage of described method is, can within a short period of time the shaping Large components with complex geometric shapes.
The solidification of epoxy resin is carried out according to different mechanism.Except with except phenol or anhydride-cured, be usually cured with amine.These materials are generally liquid and can mix admirably with epoxy resin.Due to high reactivity and therefore extremely low latent (Latenz), this composition epoxy resin is prepared with the form of two component.This means resin (A-component) and solidifying agent (B-component) separately stores and only at once just mixes with correct proportions before the use.In this article, " latent " means mixture stable existence under the condition of storage limited of each component.Two components resin preparation is also referred to as so-called cold-set resin preparaton, and the solidifying agent wherein for this reason used is selected from amine or amido amine usually.
On the contrary, single-component thermosetting epoxy resin formulation is produced in advance with form namely, that is epoxy resin and solidifying agent exist with the form mixed by manufacturer.Therefore the mixing mistake of each component when using at the scene is eliminated.Latent curing agent system forms its prerequisite, and described latent curing agent does not at room temperature react with epoxy resin (can store), but is easy to reaction when heating according to energy input.For described single component epoxy-preparation, such as Dyhard RU 100 is solidifying agent suitable and with low cost especially.At ambient conditions, corresponding resin-hardener-mixture can be stored to many 12 months with operational form.
Long-term known outstanding army (Urone) are as the curing catalyst for promoting cured epoxy resin.Therefore in numerous applications, You Rong and latent curing agent such as Dyhard RU 100 combinationally uses.Therefore the Dyhard RU 100 also illustrated in many patent applications as latent curing agent combinationally uses from the different outstanding army as curing catalyst.Thus, for example, see as Publication about Document EP603131A1, EP429395A2, US2,993,044A, US3,386,956A, US3,789,071, EP2295483A1, WO2004/106402A1, WO2007/062853A1.
In addition, known semicarbazone is used for promoting the solidification by means of the epoxy resin of heat-activated curing agent (such as Dyhard RU 100) as curing catalyst.Result of study shows, similar to known outstanding army, and semicarbazone promotes the solidification (undocumented patent application DE102010020882.5) by means of the epoxy resin of thermal activation latent curing agent.Do not mention in described document that the semicarbazone of formula (I) is used for the solidification or crosslinked of epoxy resin as solidifying agent.
Regrettably, the shortcoming with the epoxy resin composition of high latent Dyhard RU 100 or other high latent curing agent is, epoxy resin composition pole is promptly solidified and produced high heat output, namely discharges high energy.When use Dyhard RU 100 and curing catalyst (such as outstanding army or semicarbazone) thus cured epoxy resin mixture time, this effect is more obvious.The described fact forms significant problem for the technician of the structure and preparation of being engaged in moulded piece, because the energy by discharging, formed body obtains internal stress according to layer thickness.Internal stress causes the crack in moulded piece, and therefore moulded piece can not realize required mechanical stability.When depending on that the heat of layer thickness exports too high, formed body can not use completely in some cases.
Composite component replacement hardware or wooden elements (such as in aerogenerator) is used to have more and more important meaning.Therefore, the manufacturer of such as aerogenerator designs the larger equipment driven by larger spinner blade.When preparing described spinner blade, must as far as possible effectively and equably distribute the heat produced in preparation method, element in the process of preparation method is not damaged by heat.When using composition epoxy resin, it comprises the Dyhard RU 100 as solidifying agent as curing system and the outstanding army as curing catalyst or semicarbazone, described requirement cannot be ensured fully, because described system pole was promptly reacted and release amount of heat within the shortest time.Although speed of response can be controlled within the specific limits by solidifying at low temperatures; But in the large-scale solid element (such as spinner blade) with large epoxy resin layer thickness, the heat built-up caused due to the heat extraction of deficiency is promptly observed in pole.Therefore cause and promote curing reaction uncontrollably.The last cause thermal damage caused thus in element.
Prepare large-scale solid structural element in order to unstressed, therefore it must as far as possible all evenly also solidify more lentamente.Uneven heat extraction use the common curing system be made up of the Dyhard RU 100 as solidifying agent and promotor only can realize described object, because can cause localized heat to gather and therefore cause uneven solidification limited extent.Described danger is there is especially when irregular element.
Therefore the object of the invention is to, be provided for controllably solidifying the Novel curing agent especially for the composition epoxy resin of the solid member with large epoxy resin layer thickness and method, and for this reason required composition epoxy resin.Described Novel curing agent or method should be solidified uniformly within the given time, and can not produce internal stress or other cause thermal damage in moulded piece to be prepared or part.
Described object is realized by the method according to claim 1 and 2 of the present invention and purposes.
Therefore, according to first embodiment, theme of the present invention is the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent for solidifying the epoxy resin with at least one reactive epoxy groups or comprising the purposes that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups
Formula (I)
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl;
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3and R
4=jointly represent alkylidene group by forming ring.
According to second embodiment, theme of the present invention still comprises for controllably solidifying the method that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups, wherein by means of the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent
Formula (I)
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl;
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3and R
4=jointly represent alkylidene group by forming ring.
Particularly preferably, in described purposes or method, composition epoxy resin does not comprise other solidifying agent, co-curing agent, curing catalyst or other catalyzer for cured epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture.
In a preferred embodiment, whole composition epoxy resin does not comprise other solidifying agent and/or co-curing agent except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone.Especially, composition epoxy resin is not containing other solidifying agent and/or co-curing agent.Common solidifying agent and/or co-curing agent are such as aliphatic series, cyclic aliphatic and aromatic amine, polyamines, amido amine, multiamide, ketoimine, mercaptan, isocyanic ester, acid anhydrides, carboxylic acid, polyphenol, aminoresin and resol and Dyhard RU 100.
Do not mean especially in this article containing other solidifying agent and/or co-curing agent, whole system altogether comprises and is less than 1 % by weight in whole composition epoxy resin content, particularly be less than 0.1 % by weight, be also more preferably less than 0.01 % by weight and the be regarded as solidifying agent of particularly preferably 0 % by weight and/or other compound of co-curing agent.
In another embodiment, curing catalyst and/or the catalyzer for cured epoxy resin is not contained according to composition epoxy resin of the present invention.Common curing catalyst and/or be such as tertiary amine, imidazoles, You Rong, the compound based on boron trifluoride, titanate compound for the catalyzer of cured epoxy resin.
Do not contain other curing catalyst and/or mean especially in this article for the catalyzer of cured epoxy resin, whole system altogether comprises and is less than 1 % by weight in whole composition epoxy resin content, particularly be less than 0.1 % by weight, be also more preferably less than other compound of the be regarded as curing catalyst of 0.01 % by weight and particularly preferably 0 % by weight and/or the catalyzer for cured epoxy resin.
In the most preferred embodiment, composition epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture not containing other solidifying agent, co-curing agent, curing catalyst and other catalyzer for cured epoxy resin.
Unexpectedly confirm, by means of the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as the solidifying agent for cured epoxy resin, particularly as unique solidifying agent (namely there is not other solidifying agent, co-curing agent, curing catalyst or other catalyzer), the controlled solidification of epoxy resin or composition epoxy resin can be carried out.Intensive research shows, composition epoxy resin can especially leniently completely solidification and particularly without the need to using heat-activated curing agent.Therefore the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture not only can be used as the curing catalyst for promoting the solidification by means of heat-activated curing agent, also can be used as solidifying agent itself, particularly can be used as unique solidifying agent.Therefore described Novel curing agent is used can also to provide the curing system be only made up of a kind of component.Therefore without the need to regulating the number of solidifying agent and promotor also without the need to mixing the composition be made up of solidifying agent and promotor in composition epoxy resin with expending before the preparation of composition epoxy resin.
Also unexpectedly show, the alkyl semicarbazone of general formula (I) or the curing performance of dialkyl group semicarbazone or its mixture are suitable with known solidifying agent (such as Dyhard RU 100), but latent in epoxy resin or composition epoxy resin is not too outstanding.The advantage of this solidifying agent is the gentle type of solidification in fact, wherein discharges less energy compared to known solidifying agent per time unit and described energy can easily be discharged.
Therefore the also purposes of preferred described type or method, wherein composition epoxy resin comprises the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture with such amount, in composition epoxy resin, produce the maximum hot-fluid of 0.05 to 0.99W/g (quality in composition epoxy resin) in the process of the solidification of described amount at the temperature of 60 to 180 DEG C, composition epoxy resin is solidified completely.
According to the present invention, composition epoxy resin preferably solidifies completely.This means especially, composition epoxy resin >=80%, preferably >=90%, more preferably >=95%, also more preferably >=98%, particularly >=99% and most preferably 100% solidifies.Therefore, particularly >=80%, preferably >=90%, more preferably >=95%, also more preferably >=98%, particularly >=99% and most preferably 100% reacts the epoxide group in the composition epoxy resin of solidification.
The number particularly <20% of the unreacted epoxide group in the composition epoxy resin of solidification, preferred <10%, more preferably <5%, also more preferably <2%, particularly <1% and most preferably 0%.Therefore the particularly stressless solidification of composition epoxy resin can be realized.In the moulded piece by using the solidifying agent being selected from semicarbazone to prepare, do not find crack or other cause thermal damage.Be solidificated in the given time and carry out equably especially, so there is no observe local superheating or heat built-up.Therefore also can be provided for the method preparing moulded piece, described method ensures high quality standard about moulded piece to be prepared.
The temperature measurement maximum heat streams such as hot-fluid differential calorimeter (DSC822e, MettlerToledo) used according to the invention, and determine that peak portion maximum value is as maximum hot-fluid.The test condition observed is needed to describe in an embodiment.
But alternatively or simultaneously, also the consumption according to solidifying agent of the present invention can be regulated like this, make to use 1 to 15 part of solidifying agent relative to 100 parts of resins, preferably at least 3 parts and very particularly preferably at least 4 parts, wherein similarly, simultaneously or independently of one another, particularly the highest 12 parts, particularly the highest 10 parts and very particularly preferably the highest 8 parts.The present invention also contemplated the multiple combination according to solidifying agent of the present invention or combination.
Be particularly 1-15 part according to the total amount of the solidifying agent of formula of the present invention (I), preferred 2-15 part, more preferably 2-12 part, also more preferably 3-12 part, particularly preferably 4-12 part, also more preferably 5-12 part, relative to 100 parts of resins.Resin is understood to the total amount of epoxy resin.
In another preferred embodiment, be 3-12, particularly 4-12 according to the consumption of the solidifying agent of formula of the present invention (I), preferred 4-10, also more preferably 4-8 part, relative to 100 parts of resins.
Solidification by means of the epoxy resin according to solidifying agent used in the present invention is carried out usually at the temperature of 60 to 180 DEG C.The selection of solidification value is depended on specific processing request and product requirement and can when preparing mainly due to the adjustment of curing dose and change due to adding of additive.In resin formulations, introduce energy is in which way unessential.Such as, energy can be introduced with form of heat by stove or heating unit, also can introduce energy by means of ir emitter or by microwave or other rays excite.
By adding other commercially available additives, as those skilled in the art are used for known those of cured epoxy resin, the curing performance according to preparaton of the present invention can change.
For improvement of the workability of uncured composition epoxy resin or comprise such as reactive diluent, filler, rheologic additive such as thixotropic agent or dispersing additive, defoamer, dyestuff, pigment, plasticized modifier, impact modifier or fire-proof additive for the additive of the thermomechanical property adaption demand making thermoset articles.
About the present invention, alkyl semicarbazone or dialkyl group semicarbazone are understood to have the material of the structure represented with formula (I).
According to alkyl semicarbazone of the present invention or dialkyl group semicarbazone at N
3(nitrogen adjacent with carbonyl of semicarbazone group) have at least one alkyl substituent or naphthenic substituent all the time.Correspondingly, in the compound of general formula (I) according to the present invention, radicals R
1represent branching or linear alkyl or cycloalkyl, but do not represent hydrogen (R
1≠ H).R
2hydrogen can be represented.In this case, at N
3there is an alkyl or cycloalkyl in nitrogen.In another embodiment, R
2branching or linear alkyl or cycloalkyl can be represented.In this embodiment, at N
3upper existence two alkyl or cycloalkyls.
In addition, semicarbazone group with nitrogen N
1(semicarbazone group and N
2adjacent nitrogen) adjacent carbon has at least one alkyl or cycloalkyl all the time.Correspondingly, radicals R
3represent branching or linear alkyl or cycloalkyl, but do not represent hydrogen (R
3≠ H).R
4group can represent hydrogen.A branching or linear alkyl or cycloalkyl is there is in this case on the carbon of semicarbazone group.In addition, R
4branching or linear alkyl or cycloalkyl can be represented.The carbon of semicarbazone group has two alkyl or cycloalkyls in this case.Nitrogen N
2(nitrogen between carbonyl and-N=C-group of semicarbazone group) has a hydrogen substituting group all the time.But also can design like this, substituent R
3and R
4the alkylidene group with given definition is jointly represented by forming ring.Substituent R
1to R
4can extensively change in given definition.
Structurally, semicarbazone both can exist as geometrical isomer ((Z)-, (E)-isomer), also can exist with respective tautomeric forms (keto-enol tautomerism body).Depend on radicals R
1to R
4, compound obtains with the form of solid, semisolid or liquid oils.Substitute mode also determines the solubleness of semicarbazone in solvent or epoxy resin.
According to the present invention, particularly the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture can use as solidifying agent, wherein simultaneously or independently of one another:
R
1=branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl,
R
2=hydrogen, branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl,
R
3=branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl,
R
4=hydrogen, branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl;
Or
R
1=branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl,
R
2=hydrogen, branching or linear C1-to C6-alkyl or C1-to C6-cycloalkyl,
R
3and R
4=jointly represent alkylidene group by forming ring.
Alkyl or C1-to C6-alkyl can represent methyl especially, ethyl, propyl group (n-propyl), methylethyl (sec.-propyl), butyl (normal-butyl), 2-methyl-propyl (isobutyl-), 1-methyl-propyl (sec-butyl), 1, 1-dimethyl ethyl, (tertiary butyl), amyl group, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, 1, 2-dimethyl propyl, 1, 1-dimethyl propyl, 1-ethyl propyl, hexyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methyl isophthalic acid-ethyl propyl, 1-Ethyl-2-Methyl propyl group or 1, 1, 2-thmethylpropyl.
Particularly preferably such compound according to formula (I), wherein (or independently of one another) R simultaneously
1=methyl or ethyl, R
2=methyl or ethyl, and R
3=methyl, ethyl, propyl group or sec.-propyl, and R
4=methyl, ethyl, propyl group or methylethyl (sec.-propyl).
According to the present invention, R
3and R
4also jointly can represent alkylidene group, particularly C2-to C11-alkylidene group by forming ring, also preferably there is general formula-(CH separately
2)
n-(wherein 2≤n≤11), particularly-(CH
2)
nthe alkylidene group of-(wherein 2≤n≤6) or C2-to C11-alkylidene group.Can design so especially, R
3and R
4common expression ethylidene, propylidene, butylidene, pentylidene or hexylidene, wherein these alkylidene groups itself can optionally by alkyl, and particularly C1-to C6-alkyl carries out monosubstituted or polysubstituted.In this case, R
3and R
4preferably there is formula-(CHR jointly
5)
n-, wherein R
5h or C is represented independently of one another when occurring at every turn
1to C
6-alkyl.
About the present invention, cycloalkyl is also appreciated that the monocyclic cycloalkyl (C3-to C7-cycloalkyl) particularly with 3 to 7 carbon atoms, particularly has general formula C
nh
2n-1the naphthenic substituent of (wherein n=3 to 7) or C3-to C7-naphthenic substituent.Also preferably, cycloalkyl or C3-to C7-cycloalkyl can representative ring propyl group, cyclobutyl, cyclopentyl, cyclohexyl or suberyl, and wherein these cycloalkyl itself also preferably can be had the alkyl of above-mentioned implication or C1-to C6-alkyl carries out monosubstituted or polysubstituted.
Described by the preparation of semicarbazone has in the literature.Substitute mode can extensively change.A kind of common preparation method is with the synthesis ketone or aldehyde from Urea,amino-.The substitute mode of semicarbazone is determined by used reactant, wherein radicals R
1and R
2by used Urea,amino-substituting group determine, substituent R
3and R
4determined by used aldehydes or ketones.To Urea,amino-described by route of synthesis has equally in the literature.Therefore such as can according to C.Vogelesang (Rec.Trav.Chim.1943,62,5) or as described preparation 4,4-dimethylamino urea (R in WO98/47869
1=R
2=methyl) and 4,4-diethylamino urea (R
1=R
2=ethyl).Similarly, other Urea,amino-can be obtained by the reaction of hydrazine and corresponding urea chloride.Thus obtained Urea,amino-can in the end in step by changing into semicarbazone (the also reference of the expectation according to formula (I) with the reaction of corresponding aldehydes or ketones
-ZurChemieder1,3,4-Oxadiazoliumsalze, WissenschaftlicheArbeitimFachChemieander
konstanz, in June, 1994).
Such as but nonrestrictive, for alkyl semicarbazone or the dialkyl group semicarbazone of general formula (I) according to the present invention, use acetone-4, 4-dimethyl semicarbazone (Ac-DMS), methyl ethyl ketone-4, 4-dimethyl semicarbazone (MEK-DMS), bicyclo-propyl ketone-4, 4-dimethyl semicarbazone (DCyPr-DMS), methyl iso-butyl ketone (MIBK)-4, 4-dimethyl semicarbazone (MIBK-DMS), cyclopentanone-4, 4-dimethyl semicarbazone (CyPn-DMS), pimelinketone-4, 4-dimethyl semicarbazone (CyHx-DMS), acetone-4, 4-diethyl semicarbazone (Ac-DES) or cyclopentanone-4, 4-diethyl semicarbazone (CyPn-DES) is as preferably representing.
About epoxy resin to be solidified or the composition epoxy resin comprising at least one epoxy resin, the present invention does not limit.Can consider especially there is one or more than one 1,2-epoxide group (oxyethane) usually and can be saturated or unsaturated, aliphatic, cyclic aliphatic, aromatics or heterocycle all commercially available prod.Epoxy resin can also have substituting group, such as halogen, phosphorus group and hydroxyl.Based on 2, the glycidyl polyethers and 2 of 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane), the glycidyl polyethers of the derivative (tetrabromo-bisphenol) that two (4-hydroxy phenyl) propane of 2-replaces with bromine, 2, the two glycidyl polyethers of (4-hydroxy phenyl)-methane (Bisphenol F) of 2-and the glycidyl polyethers of phenolic varnish and aniline (the such as p-aminophenol or 4 based on aniline or replacement, 4'-diaminodiphenyl-methane) epoxy resin can by using according to solidifying agent of the present invention or be cured particularly well in the method according to the invention.
Therefore in embodiments of the invention, theme of the present invention is composition epoxy resin equally, described composition epoxy resin comprises the epoxy resin that a) at least one has at least one reactive epoxy groups, and b) at least one according to the solidifying agent of general formula (I) and/or the above-mentioned type.Therefore theme of the present invention is still used in particular for the composition epoxy resin preparing matrix material or moulded piece, and described composition epoxy resin comprises:
A) there is the epoxy resin of at least one reactive epoxy groups,
B) at least one is selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture
Formula (I)
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl;
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3and R
4=jointly represent alkylidene group by forming ring.
Particularly preferably such composition epoxy resin, described composition epoxy resin does not comprise other solidifying agent, co-curing agent, curing catalyst or other catalyzer for cured epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture.Also preferably, composition epoxy resin comprises and is selected from the following epoxy resin with at least one reactive epoxy groups: based on 2, the glycidyl polyethers, 2 of 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane), the epoxy resin of the glycidyl polyethers of the derivative (tetrabromo-bisphenol) that two (4-hydroxy phenyl) propane of 2-replaces with bromine, 2,2-pairs of glycidyl polyethers of (4-hydroxy phenyl)-methane (Bisphenol F) and/or the glycidyl polyethers of novolac resin.
According to a particularly preferred embodiment of the present invention, composition epoxy resin comprises with such amount and is selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture, in composition epoxy resin, produce the maximum hot-fluid of 0.05 to 0.99W/g (quality in composition epoxy resin) in the process of the solidification of described amount at the temperature of 60 to 180 DEG C, composition epoxy resin is solidified completely.
Have been surprisingly found that especially, therefore can provide such composition epoxy resin, described composition epoxy resin can carry out particularly stressless solidification and therefore be particularly suitable for preparing matrix material or moulded piece.In the moulded piece by using the solidifying agent being selected from semicarbazone to prepare, do not find crack or other cause thermal damage.Be solidificated in the given time and carry out equably especially, so there is no observe local superheating or heat built-up.Therefore also can be provided for the composition epoxy resin preparing moulded piece, described composition epoxy resin ensures high quality standard about moulded piece to be prepared.
According to preferred composition epoxy resin or method described herein or purposes, also particularly design like this according to the present invention: composition epoxy resin to comprise with such amount and is selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture, described amount is at 60 to 180 DEG C, in composition epoxy resin, the maximum hot-fluid of 0.05 to 0.99W/g (quality in epoxy resin-composition) is produced in the process of particularly 60 to 160 DEG C and solidification very particularly preferably at the temperature of 60 to 150 DEG C, composition epoxy resin is solidified completely.But also can design like this: composition epoxy resin comprises with such amount and is selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture, described amount produces the maximum hot-fluid (quality in composition epoxy resin) of 0.05 to 0.99W/g in the process of 80 to 160 DEG C, particularly 90 to 160 DEG C and the solidification very particularly preferably at the temperature of 90 to 140 DEG C in composition epoxy resin, and composition epoxy resin is solidified completely.
Simultaneously or can design so independently: adjustment is selected from the amount of the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture like this, thus 0.05 to 0.99W/g, particularly 0.05 to 0.80W/g is produced in composition epoxy resin, particularly preferably the maximum hot-fluid (quality in composition epoxy resin) of 0.05 to 0.70W/g and very particularly preferably 0.05 to 0.60W/g, makes composition epoxy resin solidify completely.
The semicarbazone according to general formula (I) (such as acetone-4,4-dimethyl semicarbazone, cyclopentanone-4,4-dimethyl semicarbazone or pimelinketone-4,4-dimethyl semicarbazone) described by majority is solid.Due to the solution property that it is good in the epoxy, described solidifying agent is particularly suitable for being solidificated in epoxy resin in the matrix material used in preimpregnation technology or composition epoxy resin.Due to the solution property that it is good, described semicarbazone is also very well adapted at preparing solid composite material elements, moulded piece in method for filling or injecting method.
But also have been surprisingly found that, liquid dimethyl-semicarbazone (such as methyl ethyl ketone-4,4-dimethyl semicarbazone and methyl iso-butyl ketone (MIBK)-4,4-dimethyl semicarbazone) not only react with epoxy resin as under the low temperature of solidifying agent between 70 and 100 DEG C at much lower concentrations, and also when reacting, per time unit discharges few heat.Therefore described solidifying agent is adapted at preparing solid composite material elements, moulded piece in method for filling or injecting method especially well.In a word, therefore the composition epoxy resin of the alkyl semicarbazone or dialkyl group semicarbazone or its mixture that comprise general formula (I) is particularly suitable for preparing matrix material and moulded piece.Especially, described composition epoxy resin is suitable for preimpregnation method, different method for filling or injecting method, particularly RTM-method.
Therefore theme of the present invention is still according to the purposes being selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture of the present invention, and the purposes in the method for solidification epoxy resin or composition epoxy resin dipping or the filamentary material be coated with, non-woven fabric, yarn fabric, knitted fabrics or cloth.
Due to the even and controlled solidification of good extremely fabulous hot-fluid and composition epoxy resin, the solidifying agent being selected from semicarbazone according to the present invention is particularly suitable for prepared layer thickness or wall is 0.5 to 500mm, the particularly moulded piece through solidification of 5mm to 400mm, particularly hollow body, particularly prepares moulded piece by means of method for filling or injecting method.
Therefore according to a special embodiment, the alkyl semicarbazone of theme of the present invention or general formula (I) or dialkyl group semicarbazone or its mixture comprise for solidifying the purposes that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups as solidifying agent, or comprise by using the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent thus solidifying the method that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups, wherein composition epoxy resin has at least 0.5mm, particularly at least 2mm, particularly at least 10mm, the particularly preferably layer thickness of at least 20mm and very particularly preferably at least 50mm.Simultaneously or therewith independently, layer thickness can be the highest 500mm.
Finally, theme of the present invention or matrix material, described matrix material comprises the composition epoxy resin of strongthener (particularly the filamentary material of carbon fiber or glass fibre or non-woven fabric, yarn fabric, knitted fabrics or cloth) and type and character described herein.
Due to the favourable application performance of solidifying agent according to the present invention and the preparation of cost advantages thereof and relevant favourable cost-benefit ratio, be applicable to industrial application and large-scale application particularly well according to solidifying agent of the present invention.
Explain the present invention hereafter by embodiment, but the present invention should not be understood to be limited to described embodiment.On the contrary, the present invention comprises the various combinations of preferred embodiment equally.
Embodiment
A) resin used
Use following as epoxy resin:
B) according to the general preparation of the semicarbazone of formula (I)
a) Urea,amino-synthesis
4,4-dimethylamino urea (R is completed by the method (such as method disclosed in C.Vogelesang (Rec.Trav.Chim.1943,62,5) or WO98/47869) known by document
1=R
2=methyl-(II)) and 4,4-diethylamino urea (R
1=R
2=ethyl-(III)) route of synthesis.The embodiment 26 of patent documentation WO98/47869 exemplarily describes, in order to prepare 4,4-dimethylamino urea (II), react in the etoh solvent under the hydrazine hydrate of equimolar amount and the cooling of dimethylcarbamyl chloride introducing ice bath and diethyl ether in the mode dripped, and react 1 hour afterwards under ice cooling, 4.After the solid of filtering-depositing, produced the target compound (II) of white crystalline solid form by concentrated reaction mixture.
B) synthesis of semicarbazone
Make afterwards to form according to Urea,amino-a) prepared the semicarbazone expected with reactive ketone.Again exemplarily choose, Urea,amino-(II) or (III) are extremely according to semicarbazone of the present invention (such as cyclopentanone-4,4-dimethyl semicarbazone (R=R
2=methyl; R
3and R
4=-(CH
2)
4-) the explanation of general available reaction.According to
(ZurChemieder1,3,4-Oxadiazoliumsalze, WissenschaftlicheArbeitimFachChemieander
konstanz, in June, 1994), cyclopentanone is reacted seething with excitement in ethanol with five times of excessive amounts and Urea,amino-(II).Reaction terminating after 45 minutes, obtains colourless to buff powder by stirring resistates under ice-cooled pentane after evaporating solvent and excessive ketone.By IR-and NMR (
1h,
13c)-spectral investigation and by CHN-analyze determine structure and composition.
Similarly be prepared in semicarbazone mentioned in this article.
C) according to solidifying agent of the present invention
D) there is the composition according to composition epoxy resin of the present invention
The composition epoxy resin with following number is such as used to show the present invention:
Epikote828 (100 parts): solidifying agent (7 parts)
E) study
I) preparation of sample
In order to prepare resin-hardener-preparation, in porcelain mortar, weighing component with given ratio and using hand Homogeneous phase mixing.
Ii) determination of gel time
In aluminium crucible, weigh the sample of the fresh preparation of about 700-800mg, described aluminium crucible is placed on (timing starts) in the heating unit be preheated to fixed temperature.Gel test is carried out by means of the fixing fillet immersing liquid resin.When producing stable silk (no longer dripping) when drawing, the described time is defined as gel time.
Iii) DSC-measurement is carried out by means of hot-fluid-differential calorimeter (DSC822e, MettlerToledo):
A) dynamic: as the temperature program(me) for determining peak temperature (DSC peak T), to be heated to for 250 (as required until 400 DEG C) with the speed of 10K/min from 30.Starting temperature is determined from identical measurement by applying tangent line to reaction peak.By carrying out integration to the area below peak from identical survey calculation energy content.
B) isothermal: in order to determine isothermal reaction time and maximum hot-fluid (peak of ISOTHERMAL DSC-measurement at a given temperature), with the speed of 20K/min, sample is heated to given target temperature T from 30 DEG C, then constant hold-time t.When hot-fluid again reaches to baseline under fixed temperature after maximum value, reaction terminating.When curve analysis time, posivtive spike corresponds to the maximum hot-fluid of curing reaction.The area of the integration below the peak of identical measurement is the energy content of reaction.Starting temperature is determined from identical measurement by applying tangent line to reaction peak.
Iv) by means of dsc measurement second-order transition temperature (final-Tg)
In order to determine accessible maximum second-order transition temperature (final-Tg), use the pre-gelled sample measured from gel time.Sample be heated to 200 DEG C (DSC-temperature program(me): 30 to 200 DEG C, rate of heating 20K/min) and keep this temperature 30 minutes thus solidify completely.Be cooled to after 30 DEG C, again sample be heated to 200 DEG C from 30 with the rate of heating of 10K/min, and apply tangent line by the flex point maximum in thermal capacity change (Δ Cp) thus determine Tg from heating curve.
V) the carrying out of latent experiment
In order to determine latent (stability in storage), fresh preparation about 10g sample and be heated to given temperature in stove.As the measuring of crosslinked gradually (solidification) of epoxy resin material, determine the dynamic viscosity of sample at 25 DEG C at each Measuring Time point boring in (1 °) plate rheometer.
Raise per-cent (%) in the viscosity in the time in hour (h) or sky (d) by being applied in and carrying out experimental evaluation by means of index or geopotential number mathematic(al) function extrapolation individual data.
Vi) the carrying out of perfusion structure:
First curing agent mixture is heated to 40 DEG C (reduction viscosity), then by means of vacuum pump (about 12mbar) drawing in fiberglass construction (three glass layers of about 0.27mm layer thickness).Once whole fiberglass construction is soaked into and added the rear suction time of a minute, cut off vacuum membrane pump.The element soaked into solidifies a few hours on hot plate at 100 DEG C.
Vii) analytical instrument used
Gel time heating unit VLM2.0HT
DSC-measures DSC-instrument Mettler-ToledoDSC822
Viscosity rheometer HaakeRheoStress1
Viii) gel time is determined, Dynamic DSC and the latent at final-Tg and 23 DEG C
Table 1: gel time, Dynamic DSC and final-Tg
At showing 2:23 DEG C in the latent in sky (d)
Ix) by means of the solidification of the matrix material of method for filling
Table 3: perfusion
Claims (15)
1. the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent for solidifying the epoxy resin with at least one reactive epoxy groups or comprising the purposes that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl, and
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl, and
R
3and R
4=jointly represent alkylidene group by forming ring.
2. comprise for controllably solidifying the method that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups, wherein by means of the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl;
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl, and
R
3and R
4=jointly represent alkylidene group by forming ring;
Wherein, described composition epoxy resin does not comprise other solidifying agent, co-curing agent, curing catalyst or other catalyzer for cured epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture.
3. comprise for controllably solidifying the method that at least one has the composition epoxy resin of the epoxy resin of at least one reactive epoxy groups, wherein by means of the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture as solidifying agent
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl;
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl, and
R
3and R
4=jointly represent alkylidene group by forming ring;
For the preparation of layer thickness or wall thickness be 0.5 to 500mm through solidification moulded piece.
4. the purposes according to claim 1 or 3 or method, it is characterized in that, composition epoxy resin does not comprise other solidifying agent, co-curing agent, curing catalyst or other catalyzer for cured epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture.
5. the purposes according to any one of claim 1-3 or method, it is characterized in that, composition epoxy resin comprises the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture with such amount, in composition epoxy resin, produce the maximum hot-fluid in 0.05 to the 0.99W/g of the quality of composition epoxy resin in the process of the solidification of described amount at the temperature of 60 to 180 DEG C, composition epoxy resin is solidified completely.
6. the purposes according to any one of claim 1-3 or method, it is characterized in that, use acetone-4,4-dimethyl semicarbazone, methyl ethyl ketone-4,4-dimethyl semicarbazone, bicyclo-propyl ketone-4,4-dimethyl semicarbazone, methyl iso-butyl ketone (MIBK)-4,4-dimethyl semicarbazone, cyclopentanone-4,4-dimethyl semicarbazone, pimelinketone-4,4-dimethyl semicarbazone, acetone-4,4-diethyl semicarbazone or cyclopentanone-4,4-diethyl semicarbazone are as according to the alkyl semicarbazone of formula (I) or dialkyl group semicarbazone.
7. the purposes according to any one of claim 1-3 or method, it is characterized in that, epoxy resin is be selected from following epoxy resin: based on 2, the glycidyl polyethers, 2 of 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane), the epoxy resin of the glycidyl polyethers of the derivative (tetrabromo-bisphenol) that two (4-hydroxy phenyl) propane of 2-replaces with bromine, 2,2-pairs of glycidyl polyethers of (4-hydroxy phenyl)-methane (Bisphenol F) and/or the glycidyl polyethers of novolac resin.
8. the purposes according to any one of claim 1-3 or method, for filamentary material, yarn fabric, knitted fabrics or cloth that solidification epoxy resin or composition epoxy resin flood or is coated with.
9. purposes according to claim 1 and 2 or method, for the preparation of layer thickness or wall thickness be 0.5 to 500mm through solidification moulded piece.
10. the purposes according to any one of claim 1-3 or method are the hollow body of 0.5 to 500mm for the preparation of layer thickness or wall thickness.
11. for the preparation of composition epoxy resin, comprise
A) there is the epoxy resin of at least one reactive epoxy groups;
B) at least one is selected from the alkyl semicarbazone of general formula (I) or the solidifying agent of dialkyl group semicarbazone or its mixture
Wherein each group represents simultaneously or independently of one another:
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl,
R
3=branching or linear alkyl or cycloalkyl; With
R
4=hydrogen, branching or linear alkyl or cycloalkyl;
Or
R
1=branching or linear alkyl or cycloalkyl,
R
2=hydrogen, branching or linear alkyl or cycloalkyl, and
R
3and R
4=jointly represent alkylidene group by forming ring;
It is characterized in that, composition epoxy resin does not comprise other solidifying agent, co-curing agent, curing catalyst or other catalyzer for cured epoxy resin except the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture.
12. composition epoxy resins according to claim 11, it is characterized in that, epoxy resin is be selected from following epoxy resin: based on 2, the glycidyl polyethers, 2 of 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane), the epoxy resin of the glycidyl polyethers of the derivative (tetrabromo-bisphenol) that two (4-hydroxy phenyl) propane of 2-replaces with bromine, 2,2-pairs of glycidyl polyethers of (4-hydroxy phenyl)-methane (Bisphenol F) and/or the glycidyl polyethers of novolac resin.
13. composition epoxy resins according to claim 11 or 12, it is characterized in that, composition epoxy resin comprises the alkyl semicarbazone of general formula (I) or dialkyl group semicarbazone or its mixture with such amount, in composition epoxy resin, produce the maximum hot-fluid in 0.05 to the 0.99W/g of the quality of composition epoxy resin in the process of the solidification of described amount at the temperature of 60 to 180 DEG C, composition epoxy resin is solidified completely.
14. matrix materials, described matrix material comprises strongthener and the composition epoxy resin according to claim 11 or 12.
15. matrix materials according to claim 14, is characterized in that, matrix material comprises the filamentary material of carbon fiber or glass fibre or non-woven fabric, yarn fabric, knitted fabrics or cloth as strongthener.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011118501.5 | 2011-11-15 | ||
| DE201110118501 DE102011118501A1 (en) | 2011-11-15 | 2011-11-15 | Alkyl or dialkyl semicarbazones as hardeners for epoxy resins |
| PCT/EP2012/072588 WO2013072354A2 (en) | 2011-11-15 | 2012-11-14 | Alkyl or dialkyl-semicarbazone as a hardener for epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103946293A CN103946293A (en) | 2014-07-23 |
| CN103946293B true CN103946293B (en) | 2016-03-02 |
Family
ID=47189933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280055597.9A Expired - Fee Related CN103946293B (en) | 2011-11-15 | 2012-11-14 | As alkyl semicarbazone or the dialkyl group semicarbazone of the solidifying agent of epoxy resin |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US9499684B2 (en) |
| EP (1) | EP2780410B1 (en) |
| JP (1) | JP6214545B2 (en) |
| KR (1) | KR101901991B1 (en) |
| CN (1) | CN103946293B (en) |
| CA (1) | CA2855897A1 (en) |
| DE (1) | DE102011118501A1 (en) |
| ES (1) | ES2643391T3 (en) |
| WO (1) | WO2013072354A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010020882A1 (en) | 2010-05-18 | 2011-11-24 | Alzchem Trostberg Gmbh | Semicarbazone for curing epoxy resins |
| DE102011118760A1 (en) | 2011-11-15 | 2013-05-16 | Alzchem Ag | Use of N, N '(-dimethyl) -units and methods for curing epoxy resin compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1574618A1 (en) * | 1988-07-04 | 1990-06-30 | Научно-производственное объединение "Полимерклей" | Adhesive composition |
| CN1242792A (en) * | 1997-10-14 | 2000-01-26 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| CN102906147A (en) * | 2010-05-18 | 2013-01-30 | 澳泽化学股份公司 | Semicarbazones as accelerators for curing epoxy resins |
Family Cites Families (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993044A (en) | 1958-12-19 | 1961-07-18 | Monsanto Chemicals | Diureides and method for their preparation |
| US3274231A (en) | 1962-09-13 | 1966-09-20 | Asahi Chemical Ind | Compositions and methods of stabilizing unsaturated organic nitriles |
| US3386955A (en) | 1966-01-14 | 1968-06-04 | American Cyanamid Co | Substituted ureas as low temperature epoxy curing agents |
| US3454669A (en) | 1966-10-13 | 1969-07-08 | Lubrizol Corp | Novel epoxy curing agents |
| GB1153639A (en) | 1966-12-30 | 1969-05-29 | Ciba Ltd | Epoxide Resin Compositions |
| FR1570670A (en) | 1968-04-19 | 1969-06-13 | ||
| US3753680A (en) | 1970-05-14 | 1973-08-21 | Stauffer Chemical Co | Arylidene semicarbazones and their utility as herbicides |
| US3717612A (en) | 1970-06-22 | 1973-02-20 | Hitco | Curable epoxy resin composition containing a substituted diurea compound |
| US3789071A (en) | 1971-10-07 | 1974-01-29 | Hitco | Epoxy curing agent |
| BE795111A (en) | 1972-02-09 | 1973-08-07 | Philips Nv | BENZYLIDENE-SEMICARBAZIDE COMPOUNDS AND THEIR INSECTICIDAL ACTIVITY |
| DE2236339A1 (en) | 1972-07-25 | 1974-02-07 | Bayer Ag | Alpha-cyano-hydrazones preparation - with pre and post-emergence herbici-dal activity |
| CH637411A5 (en) | 1979-04-20 | 1983-07-29 | Ciba Geigy Ag | EPOXY RESIN, HARDENER AND HARDENING ACCELERATOR CONTAINING, STORAGEABLE HOMOGENEOUS MIXTURE AND THE USE THEREOF FOR THE PRODUCTION OF HARDENED PRODUCTS. |
| US4360649A (en) * | 1980-04-30 | 1982-11-23 | Sumitomo Chemical Company, Limited | Curable composition |
| JPS57185316A (en) | 1981-05-11 | 1982-11-15 | Sumitomo Metal Mining Co Ltd | Electrically conductive resin paste |
| JPS5885238A (en) * | 1981-11-16 | 1983-05-21 | 田岡化学工業株式会社 | Method of producing tubular fuse |
| JPS6011458A (en) | 1983-06-30 | 1985-01-21 | Showa Denko Kk | Semicarbazide and semicarbazone derivative and herbicide |
| SU1502585A1 (en) | 1987-05-08 | 1989-08-23 | Ленинградский Технологический Институт Им.Ленсовета | Pulverulent compound for obtaining foam plastic |
| US4804740A (en) | 1987-07-08 | 1989-02-14 | Amoco Corporation | Cyanate ester with urea latent cure accelerator |
| EP0429395B1 (en) | 1989-11-21 | 1995-03-29 | Ciba-Geigy Ag | Curable epoxy resin composition containing a latent curing agent, an amine and a thiol |
| US5043102A (en) * | 1989-11-29 | 1991-08-27 | Advanced Products, Inc. | Conductive adhesive useful for bonding a semiconductor die to a conductive support base |
| EP0462456B1 (en) | 1990-06-16 | 1996-05-08 | Nihon Nohyaku Co., Ltd. | Hydrazinecarboxamide derivatives, a process for production thereof, and uses thereof |
| EP0603131A1 (en) | 1992-12-18 | 1994-06-22 | Ciba-Geigy Ag | Aromatic urea compound used as hardening accelerator for a composition of epoxy resin and dicyandiamide |
| FI941593A (en) | 1994-04-07 | 1995-10-08 | Leonid Nikolayev Machliakovski | Powder composition for coatings |
| GB2300187B (en) | 1995-04-28 | 1998-09-02 | Hodogaya Chemical Co Ltd | Cure-accelerator for epoxy resin |
| JPH09323969A (en) * | 1996-06-03 | 1997-12-16 | Asahi Chem Ind Co Ltd | Semicarbazide-based composition |
| WO1998047869A1 (en) | 1997-04-22 | 1998-10-29 | Cocensys, Inc. | Carbocyclic and heterocyclic substituted semicarbazones and thiosemicarbazones and the use thereof |
| JP4033518B2 (en) * | 1997-04-24 | 2008-01-16 | 旭化成ケミカルズ株式会社 | Novel semicarbazide compound and coating composition using the same |
| JP2003039505A (en) | 2001-07-27 | 2003-02-13 | Koyo Seiko Co Ltd | Resin molded object, method for molding the same and mold therefor |
| JP2004256729A (en) | 2003-02-27 | 2004-09-16 | Kyocera Chemical Corp | Epoxy resin composition and sealed semiconductor device |
| DE10324486A1 (en) | 2003-05-30 | 2004-12-16 | Degussa Ag | Use of urea derivatives as accelerators for epoxy resins |
| JP2005042023A (en) * | 2003-07-23 | 2005-02-17 | Asahi Kasei Chemicals Corp | Semicarbazide hardener composition |
| CA2545011A1 (en) * | 2003-11-14 | 2005-05-26 | Basf Aktiengesellschaft | Cis-trans isomerisation of semicarbazone compounds |
| JP2006152170A (en) | 2004-11-30 | 2006-06-15 | Nichias Corp | Conductive epoxy resin composition and preparation process of the same |
| EP1710286A1 (en) | 2005-04-04 | 2006-10-11 | 3M Innovative Properties Company | Reinforcement Pad |
| DE102005057590A1 (en) | 2005-12-02 | 2007-06-06 | Degussa Ag | Use of 1- (N'-cyanoguanyl) derivatives of N-containing five-membered heterocycles as curing agents for epoxy resin compositions |
| JP5138239B2 (en) | 2007-02-22 | 2013-02-06 | ニチアス株式会社 | Resin composition for fuel cell separator and fuel cell separator |
| JP5327583B2 (en) | 2008-08-01 | 2013-10-30 | ニチアス株式会社 | Resin composition for fuel cell separator and fuel cell separator |
| US8076395B2 (en) | 2009-09-11 | 2011-12-13 | Air Products And Chemicals, Inc. | Low temperature curable epoxy compositions containing urea curatives |
| CN101709195A (en) | 2009-12-25 | 2010-05-19 | 广州擎天实业有限公司 | Pure epoxy powder coating for coating bakelite board and preparation method thereof |
| DE102011118760A1 (en) | 2011-11-15 | 2013-05-16 | Alzchem Ag | Use of N, N '(-dimethyl) -units and methods for curing epoxy resin compositions |
-
2011
- 2011-11-15 DE DE201110118501 patent/DE102011118501A1/en not_active Withdrawn
-
2012
- 2012-11-14 US US14/357,049 patent/US9499684B2/en active Active
- 2012-11-14 ES ES12787434.5T patent/ES2643391T3/en active Active
- 2012-11-14 CN CN201280055597.9A patent/CN103946293B/en not_active Expired - Fee Related
- 2012-11-14 KR KR1020147012798A patent/KR101901991B1/en active IP Right Grant
- 2012-11-14 CA CA2855897A patent/CA2855897A1/en not_active Abandoned
- 2012-11-14 WO PCT/EP2012/072588 patent/WO2013072354A2/en active Application Filing
- 2012-11-14 EP EP12787434.5A patent/EP2780410B1/en active Active
- 2012-11-14 JP JP2014541638A patent/JP6214545B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1574618A1 (en) * | 1988-07-04 | 1990-06-30 | Научно-производственное объединение "Полимерклей" | Adhesive composition |
| CN1242792A (en) * | 1997-10-14 | 2000-01-26 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| CN102906147A (en) * | 2010-05-18 | 2013-01-30 | 澳泽化学股份公司 | Semicarbazones as accelerators for curing epoxy resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015501854A (en) | 2015-01-19 |
| WO2013072354A3 (en) | 2013-08-29 |
| CA2855897A1 (en) | 2013-05-23 |
| US9499684B2 (en) | 2016-11-22 |
| US20140308863A1 (en) | 2014-10-16 |
| KR101901991B1 (en) | 2018-09-28 |
| WO2013072354A2 (en) | 2013-05-23 |
| CN103946293A (en) | 2014-07-23 |
| EP2780410A2 (en) | 2014-09-24 |
| JP6214545B2 (en) | 2017-10-18 |
| DE102011118501A1 (en) | 2013-05-16 |
| KR20140100471A (en) | 2014-08-14 |
| ES2643391T3 (en) | 2017-11-22 |
| EP2780410B1 (en) | 2017-09-06 |
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